Generation of synthesis gas



Dec. 20, 1949 E, w, RlBLETT I 2,491,518

GENERATION OF SYNTHESIS GAS Filed April 1l, 1947 `r 'ar/ i/eff BY M ATTORNEY .the presence of an iron catalyst. Itls 'We1l `to stress that this commercial operation depends-'on Aduring the generation of synthesis l`Equation A covers the desired reaotio 'tions which are promoted by e'ley acquainted, corroborated predioti Patented Dec. 2.0,

UNITED -ST'S PATENT OFFICE poration of New Jersey Appiic'afibn iran 11, 19217, sfifi e. 740,836

5 claims. (c1. 252-373) This invention relates to a process'fr thelp'roduction of synthesis gas, i.. e., agas mikture oo nsisting essentially of carbon monoxide and -hydrogen, suitable for charging to a synthslsreaotion zone for the production of hydroo':' a.`rbo ns,"n oxygenated compounds and the like.

ticularly, the invention relates to a` producing synthesis gas by reacting` 'a I bon and oxygen of high purity atanv elevated pressure.

The catalytic synthesis of hydroarbons and oxygenated compounds like alcohols and ketoies hasin the last decade been the sub'ec't of extensive research from .whichvnoteworthy 'improvements have stemmed. Y research has nated in the development of a'comx'x'ieroal process involving the production of high-quality gasoline vhydrocarbons by reacting carbon iiox'ioidead hydrogen at elevated pressure and teipertifin conducting the syntl'iesisl re'actioi at 'l'toted pressure, say 200 to 300 lbs." 'pe`r"`sq. infgaige.

' will be more readily appreciated from' a oo'rsde'ition of several reactions which matak'ploe gas a'rd'wl'iiohf using methane for the sake of simplest eif 'pliikcation, may be expressed by the follovsfingeqations:

(A) 2CH4+O2=2CO+4H3 (B) CO+3H2=CH4+H2 (C) 2CO+2H2=CH4 +`CO2 (D) 2CO+O2=2CO2 (E) 2CO=CO2+C aigle 2 efltors -filled with refractory and/or catalytic packing material would choke up with deposited carbon Within a. few hours when operated at high pressure, necessitating a shut-down and cleaning `-ofthe generator.

It isfan'object of this invention to provide'. a commercially feasible process for.v the production lo`f synthesis: gas by reacting a hydrocarbon and `high-"purity .oxygen at elevated pressure While wldelimiiating .or avoiding. substantially completely the formation -of carbon.

related object is to Aproduce synthesis gas `at "high pressure with very efficient utilization of the reactant hydrocarbon and oxygen. A V|Ihese a'.' "d4 other objects .of my inventionwill bei apparent .in thedescription which follows..

'In accordance with the invention, one or more hydrocarbons, preferably normally gaseous. hy- "drocarbons,arereacted in vapor phase with oxygen of not vless thanabout 95% (by volume) purity', preferably. not.1ess than 98% purity, in such 'iroportionsthat the resulting synthesis gas contains less Athanabout 5.0% by volume of. carbon dioxide', preferably. less than about 2.0%, and le'ss tliln'l'about 5.0% by volumeV of unreacted or resid- *ual hydrocarbon, 'preferablyless than .about 2.0%. The reaction zone is generally. maintained. at-a temperature. above .2000 temperaturesin .the

'range' of' 2100to 25009 F. being particularly ad- ...80.

"v'antageous, -Thereaction is conducted under-la "pressure of" 10D-to 500 lbs. per sq. in. gauge, pref- `-enably about 200 to 300 lbs. per sq. in. gauge. .To eieotate the purposes of the invention, control 'ofthe fo'i'e'go'ing conditions is coupled with a pro- "35 v:longatih or extension of the contact time. The

exo

"'"iimum effective contact time is at least about ""loib'le' the 'contact time required for conducting 'me reaction (i. e., same reactants, propor- "tions','teii attire, etc.) at atmospheric pressure; "pressures aboye 200 lbs. per sq. in. gauge, the "oritt" iie preferably is madey about threefto tir'isthat employed at atmospheric presand oxygen to produce synthesisga's bii .Qeraiti'rig in accordance with the foregoing from an examination 0f this .quti T' .,llli ,I. @alle @und that the OXYgn. 1S 11?- pressure Will favor thel reversefrea tion r 'stanti'a completely reacted (the QXygQn ,-CQII1 'versely, willsuppre'ss the desired 't 1""" t'nt ofthe product synthes1s gas 1s rarely as tions B to F represent ve ides Extensive experimentation',. with li such theoretical considerationsca bo s. stetige.- 't'ion was particularly serious. Syn ss 'sntact time and elevated pressure should normally favor poor conversion of hydrocarbon and oxygen to carbon monoxide and hydrogen as indicated by Equations A, B and C and, in turn, unconverted available oxygen under the same conditions should promote the formation of carbon dioxide and water as shown by Equations D and F, respectively, with consequent impairment of the utilization of the reactants in the production of carbon monoxide and hydrogen. These severe reaction conditions should also increase the formation of carbon not only because of the tendency represented by Equation E but also because unreacted available hydrocarbon (per Equation A) and, more particularly, reformed methane (per Equations B and C) are susceptible to degradation to carbon and hydrogen on prolonged exposure to elevated temperatures above 2000 F. That the oxygen used in my process is substantially completely consumed is of prime signincance not only in terms of economic utilization of a fairly expensive feed material but also as regards the product synthesis gas which is subsequently passed to a catalytic synthesis zone to form hydrocarbons and/ or oxygenated compounds. A synthesis gas having more than a trace of free oxygen is commercially unattractive since the oxygen will oxidize the synthesis'catalyst, particularly an iron catalyst, eiecting undesired changes in the quality and quantity of the products synthesized and necessitating frequent reduction or regeneration of the synthesis catalyst. Synthesis gas produced by the process of my invention is particularly well suited for direct charging to a catalytic synthesis reactor Vwithout intermediate treatment except cooling to a temperature level near that maintained in the synthesis reactor.

As is known, the reaction (Equation A) by which synthesis gas is produced is not strongly exothermic so that to support a reaction tem- .perature above 2000 F. without burning in situ a considerable proportion of the feed hydrocarbon to carbon dioxide, the reactant hydrocarbon land oxygen are preheated to an elevated tem- ``perature of at least about 600 F., preferably at lleast about 1000" F. When preheating to temperatures up to about 700 F., the reactants may nbe preheated as a mixed stream or as separate l.

'streams but when higher preheat temperatures ,are desired, preheating is advantageously applied i'to the separate reactant streams. Preheating of the hydrocarbon stream is advisably limited to a temperature level at which no substantial crack- .ing or degradation to free carbon is encountered. With the indicated preheating of the reactants and operating in a reaction system which does not have excessive heat losses, I nd it is possible to maintain a reaction temperature above 2000 F. i

`Yand obtain a synthesis gas containing less than about 5.0% by volume of carbon dioxide and less than about 5.0% by volume of unreacted hydrocarbon. The limited presence of carbon dioxide shows that no substantial proportion of the re-:. actants has been consumed in the formation of this undesired by-product and the limited presence of unreacted hydrocarbon points to a j high conversion in spite of the limited amount of heat liberated in situ by the formation of carfbon dioxide. '0 The term, contact time, as used in this specifi- 'cation and the appended claims is intended to mean the time during which the reactant hydrocarbon and oxygen are exposed to the specified.

reaction conditions and is not bound to any 'through the reaction zone notion of contact with a catalytic or other r# active surface even though, if desired, the reaction may be conducted in a zone lled with catalytic or refractory packing' material. From experience, I prefer to use a reactor free of packing material for two reasons. First, packing usually offers some resistance to the flow of the gaseousreactants with the result that some of the reactants diluse through the refractory lining within the reactor, reacting exothermically between the lining and metal shell and thus creating dangerous hot spots on the walls of the high-pressure reactor. Second, packing, under the conditions followed in my process, appears to magnify any tendency to carbon formation arising from accidental or unavoidable fluctuations in the operation; there is evidence that a little carbon deposited on packing material beg'ets more carbon with cumulative propensity. Accordingly, I strongly favor using an empty or unpacked reactor.

To describe and clarify my invention more fully reference is made to the accompanying drawings of which:

Figure 1 is a schematic representation of a simple form of apparatus suitable for carrying out the process of my invention; and

Figure 2 is a schematic representation of another form of apparatus suitable for my purposes and featuring the recovery of heat from the product synthesis gas in preheating the reactants.

Referring to Figure 1, the numeral I 0 designates an upright cylindrical generator comprising a metal shell I I suitable for withstanding elevated pressures and a refractory lining I2 forming aninternal reaction zone I3 in which synthesis gas is generated. The reactants are fed into the lower portion of reaction zone I3 through the nozzle I4 which comprises a. tube I5 and a concentric, smaller tube I 6. One reactant stream is fed through the inner tube I6 while the other reactant is fed through the annular space between the concentric tubes I5 and I6. The reactants are thoroughly mixed on discharging from the open end of the nozzle I4 and immediately proceed to react while owing upwardly I3. The product syn-` thesis gas discharges from the generator I 0 by way of opening I7 into piping and other equipment (not shown) for the cooling and utilization of the synthesis gas, as desired. The hydrocarbon reactant stream, e. g., natural gas supplied by line I8, flows through a preheater I9 and passes by way of line 20 into the annular space betweenconcentric tubes I5 and I6 of nozzle I 4. At the same time the oxygen stream supplied by line 2I flows through preheater 22 and passes by way of line 23 into the inner tube I6 of nozzle I4. The hydrocarbon stream discharging from the annular portion of nozzle I4 and the oxygen stream discharging from the central portion of nozzle I4 become intimately mixed in the lower portion of reaction zone I3 and immediately proceed to react while'ilowing toward the outlet I1 of generator I 0.

Referring to Figure 2, the numeral 30 desig -nates a generator comprising a metal shell 3| with convex ends 32 and 32 provided respectively with outlet openings 33 and 33. Generator 30 is lined with a refractory material 34 to -protect the metal shell 3I against the high temperatures developed within the generator. The Vinterior of generator 30 is divided into a central reaction zone 35 and two adjoining heat-regen erativezones 36. and 36 containingheat-absorp'r tive -che'ckerwork. or similar heat-absorptive bodies. Theoutlets-33.- and 33 are. connected respectively to. manifolds-.31 and 31 which in turn arefconnected. with manifolds 38 and 3S. The manifolds 38 and 33 are each providedwitha pair of valves. 38A and 38B and 39A and 39B, respectively.. Another manifold 40 having valves 40Aand-40B-isconnected-to inlet openings 4I and 4I which discharge intothe reaction zone 35 of generator 30. Asshown, natural gas or other desired. hydrocarbonfeed flows through line 42 into-heat exchanger 43 and passes by way of line 44 into manifold 40while the product synthesis gasV discharges from manifold 39 by Way of line 43=intoheat exchanger 43:- and thence passes through .hlin e 46 toany desired equipment (not shown) for cooling andwutilizing the product gas. At `the Sametime oxygen owing through line. 41 enters-the manifold 38. The operation of this regenerativesystem readily described in terms of twofcycles, which, for convenience, will be referredto as cycle AK and cycle B. During cycle A, valves-38A, 39A and 40A are'open While valves 38B, 39B and 40B are closed. With this valve setting. oxygen-4 from 41 flows through manifold 38 and. valve 38A, manifold. 31 and inlet. opening.,l 33 into heat-regenerative vzone 36. l, Naturalt'. gas preheated. by indirect heat exchange with the product synthesis gas inV exchanger 43.flows. through-line, manifoldA 40 andrvalve 40A. and inlet opening 4I into the reaction zona-35.- This hydrocarbon stream intermingleS-withthe oxygenstream preheatedin heatregenerative zone 36 andA as a reacting mixe ture'ows across the reaction zone 35-enterng the.heati-regenerativezoneV 36' when the reaction has been substantially completed. The hot reaction.gasesthat is, the product synthesis gas, gives up.some of its heat to the heat-absorptive packing in. heat-regenerative zone 36' and discharges ina partially'cooled'condition through outletopening33, manifold 31', manifold 39 and. valve. 39A.and line 45 into heat exchanger 43 where the synthesis gas gives -up additional heat to theincominghydrocarbon feed stream. From heat exchangerv 43the=synthesis gasl proceeds to any-desiredpoint of utilization. rlhe duration of theoperationof cycle A-is, ofcourse, dependentv upon the heat-absorbing capacity of the regenerative zones 36' and- 36. Thus, when the incomingoxygenstream can'no longer be effectivelyfpreheated byheat stored within regen-v erative. zone 36 and thehotproduct gas can no longer-be effectively cooled by regenerative zone 36?, cycle=A is terminated and'at the same time oycleBis initiated. DuringI cycle-B Valves 38B, 39Bfandr40B-are open while-valves 38A, 39A and 40A are closed. With this valve setting oxygen owsxthrough manifold 38 and valve 38B, manifold 31 and opening 33 into heat regenerative zone 36'. Thefoxygenows-through zone 36' and isfpreheated by theheatstored up inv this/zone by the hot product gas during the previouscycleA A. At the same time the hydrocarbon stream, preheated'in exchanger 43, flows through line 44, manifolch 40 and valve 40B,.and inlet 4I. into: reaction' zone 35 adjacent the region where'pre'- heated. ox-ygen discharges from zone 36 into-zone 35. The mixed reactants flow across reaction zone 35 and in substantially completely reacted condition enter heat-regenerative zone 36. The reaction gases on flowing through heat-absorptive packing within zone 36 are partially cooled and thence pass through opening 33, manifold uous by repeating. cycles A and B in succession.-

Ordinarily, regenerative systemsv are designed for operation in cycles of three to ten minutes, preferably about three to five-minutes.

As a specific example of the operation described in connection With the apparatus of Figure 1, the following data are given. The generator I0 has an internalfree space-or reactionzone I3 of 1000 cubic feet. Natural gas and oxygen are` separately preheated to a temperature of 1000 F. by heatersv I9 and 2-2, respectively. The approximate composition of the natural gas is:

Per centby volume C1 hydrocarbon 84.1' C2 hydrocarbons 10.3 C3 hydrocarbons 4.5 C4 hydrocarbons 0.1 CO2 1.0i

The preheated reactants arev chargedv to the generator at the rates of 836,000 cubic feet of natural gas per hour and 565,000 cubic feet of oxygen per hour, both rates being measured at standard con` ditions. The reactants under good mixing conditions enter reaction zone I3 maintained atv a pressure of 250 lbs. per sq. in. gauge and immediately start to react whilel flowing to outlet I1. The reaction temperature is about 2500 F. as measured in the gaseousproduct stream passing through outlet I1. The contact time under these circumstances iscalculated to be 6 seconds; this contact time is approximately three times that necessary for generating synthesis gas at atmospheric pressure under otherwise similar conditions; The product gas discharging from outlet I1'is free of carbon particles and has the following composition calculated on the dry basis:

Per cent by volume CO 35.71 H2 60.3 CO2 1.3 CH4 2.7

I may elect to operate the generator. at a lowerf or higher feed rate than that of the foregoing example. At a lower feed rate; the utilization eiciency of both carbon and oxygen is increased atthe expense of higher investment' costsv for the larger equipment requiredfor thelower through-A put. Thus-,by doubling the contact time and leavingall the other factors inthe foregoing examplel unchanged, a synthesis gas is produced which is still free-of' carbon particlesand which on the-dry basis has the followingzcomposition:

Per cent by volume CO 35.7 Hz 61.1 CO2 1.2 CH4 2.0

,hydrocarbons.

In this case, the utilization emciency on the carbon basis is nearly 92% and on the oxygen basis is about 82.5%.

Mention has been made of charging methane or a gas consisting essentially of methane to the generator. It is contemplated, however, that the hydrocarbon charge to the generator may comprise higher molecular weight hydrocarbons either normally gaseous or normally liquid. The

hydrocarbon charge may consist essentially of normally liquid hydrocarbons or it may comprise a combination of gaseous and normally liquid For the purposes of this invention, liquid hydrocarbons may embrace not only relatively high boiling hydrocarbon mixtures boiling in the range of fuel oil but also asphalt and other solid hydrocarbons which melt and ilow when heated.

Higher molecular weight hydrocarbons when charged to the generator undergo some decomposition into lower molecular weight products including methane. Furthermore, the gases in the generator tend to produce some methane in accordance with Equations B and C hereinbefore presented. Therefore, when charging higher hydrocarbon homologs, the regulation of the proportions of oxygen and hydrocarbon in the feed to yield a synthesis gas containing less than about by volume of unreacted or residual hydrocarbon (whether it is the charged hydrocarbon or reformed methane, is immaterial), preferably less than about 2%, is still a. valid guide. In all cases, I have found that to decrease the proportion of oxygen fed to the generator to a point such that the product synthesis gas contains more than 5% by volume of hydrocarbon leads to a noticeable formation of free carbon. While I prefer to supply enough oxygen to reduce the the oxygen. On the basis of the carbon content,

a utilization efiiciency of at least about 80% and frequently about 90% or over is realized for the hydrocarbon feed.

Obviously, many modifications and variations of the invention as above set forth may be made Without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

What I claim is:

1. The improved process for generating synthesis gas substantially free of carbon, which comprises preheating a hydrocarbon and highpurity oxygen to a temperature of at least about 600 F., charging the preheated reactants into a reaction zone maintained at a temperature above about 2000 F. but not exceeding about 3000 F. and a pressure in the range of about 100 to 500 lbs. per sq. in. gauge, regulating the proportions 0f the charged reactants and the contact time f said reactants in said reaction zone within the range of about 1 to 20 seconds, so that the product synthesis gas contains not more than about 5% by volume of carbon dioxide and not below about 0.5% but not more than about 5% by volume of hydrocarbon and is substantially free of carbon, said contact time being at least double the contact time required to generate synthesis gas substantially free of carbon when said reaction zone is at atmospheric pressure, and withdrawing the product synthesis gas from said reaction zone.

2. The process of claim 1, wherein the hydrocarbon is predominantly methane.

3. The improved process for generating synthesis gas substantially free of carbon, which comprises preheating a hydrocarbon and-.highpurity oxygen to a temperature of at least about 600 F., charging the preheated reactants into a reaction zone maintained at a temperature above about 2000 F. but not exceeding about 3000 F. and a pressure in the range of about 200 to 300 lbs. per sq. in. gauge, regulating the proportions of the charged reactants and the contact time of said reactants in said reaction zone within the range of about 3 to 10 seconds so that the product synthesis gas contains not more than about 5% by volume of carbon dioxide and not below about 0.5% but not more than about 2% by volume of hydrocarbon and is substantially free of carbon, said contact time being about three to four times the contact time required to generate synthesis gas substantially free of carbon when said reaction zone is at atmospheric pressure, and withdrawing the product synthesis gas from said reaction zone.

4. The process of claim//Wherein the hydrocarbon is predominantly methane.

5. The improved process for generating synthesis gas substantially free of carbon, which comprises preheating methane an( high-purity oxygen to a temperature of at least about 600 F., charging the preheated reactants into a reaction zone maintained at a temperature above about 2000 F. but not exceeding about 3000 F. and a pressure in the range of about 200 to 500 lbs. per sq. in. gauge, regulating the proportions of' the charged reactants and the contact time of said reactants in said reaction zone within the range of 1 to 20 seconds so that the product synthesis gas contains not more than about 2% by volume of carbon dioxide and about 0.5 to 2% by volume of methane and is substantially free of carbon, said contact time being'at least double the contact time` required to generate synthesis gas substantially free of carbon when said reaction zone is at atmospheric pressure and withdrawing the product synthesis gas' from said reaction zone.

EARL W. RIBLE'IT.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 1,843,063 vBurke Jan. 26, 1932 2,051,363 Beckley Aug. 18, 1936 

